Platinum (ii) emitters for oled applications

ABSTRACT

Described herein are novel platinum(II) emitters. These materials show high emission quantum efficiency, a low self-quenching constant and are stable in thermal deposition process. Organic light-emitting diodes (OLEDs) fabricated from these materials can have pure green emission, high efficiency and low efficiency roll-off. The OLEDs can have a chemical structure of:

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of application Ser. No. 14/243,950filed on Apr. 3, 2014, the entire contents of which are incorporatedherein by reference.

TECHNICAL FIELD

Described herein are class platinum(II) emitters their preparation andapplications in organic light-emitting diode (OLED).

BACKGROUND

Even platinum is better than iridium in natural abundance and cost,nowadays, only iridium(III) emitters are used OLED display panels. Manyremaining issues have to be solved before platinum(II) emitters can beused in OLED display panel production. Efficiency roll-off is one of themost important issues encounter by platinum(II) emitters. It is becauseplatinum emitters adopt a square planar geometry and the platinumcenters tends to come together, platinum(II) emitters usually have veryhigh self-quenching constants (in the order of 10⁸ dm³ mol⁻¹ s⁻¹ ormore). Together with the long emission lifetime (near or longer than 10μs), the devices fabricate from platinum(II) emitters usually havesevere triple-triplet annihilation leading to serious efficiencyroll-off.

Limited by the low emission quantum efficiency, OLEDs fabricated fromplatinum(II) emitter have shown related low efficiency. In the pastdecade, due to the improvement in emission quantum efficiency, themaximum device efficiency of 51.8 cd/A has been achieved by platinum(II)emitters [Appl. Phys. Lett. 91, 063508 (2007)]. However, theefficiencies of these device drops to less than 50% of the maximumvalues when the brightness increased to acceptable operation brightnesssay 1,000 cdm⁻². This is not good for OLED applications.

Besides serious efficiency roll-off, OLEDs fabricated from emitterswhich tend to come together (in the other words: tends toself-aggregate/have high self-quenching constant) always have narrowdoping window (devices with high efficiency and good color purity canonly be obtained in a very narrow doping concentration range such as 1wt. %-5 wt. %). As the fabrication systems in industry are much largethan those in research institutes, making devices within such narrowdoping window is not an easy task. As a result, platinum(II) materialsare not yet been used in industry.

Some efforts have been made to deal with this issue. Bulky groups suchas tert-butyl group(s) and non-planar phenyl group have been added tothe emitters. However, they are not successful. In 2010, Che addedtert-butyl group(s) in red-emitting platinum(II) material. [Chem. Eur.J. 2010, 16, 233-247] However, close intermolecular stacking π-πinteractions were still observed in the X-Ray crystal structure whichmeans the problem cannot be resolved.

In the same year, Huo report a class of platinum(II) materialscontaining a non-planar phenyl ring, however excimer emission appears indoping concentration more than 4 wt. % and severe triplet-tripletannihilation was observed even in a device with a mix host, which meansthis approach cannot solve the problem [Inorg. Chem. 2010, 49,5107-5119].

In 2013, Xie prepared new emitters containing two non-planarspiro-structures. [Chem. Commun. 2012, 48, 3854-3856] However, thedevices fabricated by this emitter show serious efficiency roll-offof >50% which indicates adding non-planar group(s) may able to reduceroll-off.

In the same year, Che combined the two approaches and using a new,robust (ÔN̂ĈN) ligand system to prepare new platinum(II) materials. Inthis approach, one of the emitters shows a wide doping window and slowefficiency roll-off [Chem. Commun. 2013, 49, 1497-1499]. However, thequenching constants of these materials are still high (minimum value:8.82×10⁻⁷ dm³ mol⁻¹ s⁻¹) which made the maximum efficiency of the deviceonly achieve 66.7 cd/A, whereas even the emission quantum efficiency ofthe device is 90%. Close or more than 100 cd/A should be obtained withthis emission quantum efficiency if the quenching effect is resolved.

SUMMARY

In this invention, we design platinum(II) emitters with a new ligandcore which have high emission quantum efficiencies, small self-quenchingconstants. They are ready to be used in industry.

The invention relates to novel platinum(II) emitters having the chemicalstructure of Structure I. Also provided are methods of preparing theplatinum(II)-based materials, and their applications in organiclight-emitting diode (OLED).

In one embodiment, the platinum(II)-based compounds of Structure I areshown as follows:

wherein R₁-R₁₃ are independently hydrogen, halogen, hydroxyl, anunsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstitutedaryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro,acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl,carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group.Each pair of adjacent R groups of R₁-R₁₃ can independently form 5-8member ring(s) with 2 or 4 carbon atoms in the phenyl ring(s) showed inStructure I; B and

are self-quenching reduction groups.

The invention also provides devices fabricated from the platinum(II)emitters of Structure I. Advantageously, the devices of the inventionexhibit at least one of and often both of high efficiency and lowroll-off. Pure green emission can also be obtained in this materialsystem.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: Synthetic Scheme of the Emitters.

FIG. 2: X-Ray structure of Emitter 1002.

FIG. 3: UV-Vis absorption and emission spectra of Emitter 1002.

FIG. 4: Current density—voltage graphs of the OLEDs fabricated fromEmitter 1002.

FIG. 5: Luminance—voltage graphs of the OLEDs fabricated from Emitter1002.

FIG. 6: Power efficiency-luminance graphs of the OLEDs fabricated fromEmitter 1002.

FIG. 7: EL spectra of the OLEDs fabricated from Emitter 1002.

FIG. 8: Efficiency cures of the OLEDs fabricated from Emitter 1002.

FIG. 9: The optimized geometries of Emitter 1002

FIG. 10: Frontier MO diagram of Emitter 1002

FIG. 11: Time-resolved fluorescent of Emitter 1002 in CH2Cl2 withexcitation at 350 nm.

DETAILED DESCRIPTION

Definitions

To facilitate the understanding of the subject matter disclosed herein,a number of terms, abbreviations or other shorthand as used herein aredefined below. Any term, abbreviation or shorthand not defined isunderstood to have the ordinary meaning used by a skilled artisancontemporaneous with the submission of this application.

“Amino” refers to a primary, secondary, or tertiary amine which may beoptionally substituted. Specifically included are secondary or tertiaryamine nitrogen atoms which are members of a heterocyclic ring. Alsospecifically included, for example, are secondary or tertiary aminogroups substituted by an acyl moiety. Some non-limiting examples of anamino group include —NR′R″ wherein each of R′ and R″ is independently H,alkyl, aryl, aralkyl, alkaryl, cycloalkyl, acyl, heteroalkyl, heteroarylor heterocycyl.

“Alkyl” refers to a fully saturated acyclic monovalent radicalcontaining carbon and hydrogen, and which may be branched or a straightchain. Examples of alkyl groups include, but are not limited to, methyl,ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-heptyl, n-hexyl,n-octyl, and n-decyl.

“Alkylamino” means a radical —NHR or —NR₂ where each R is independentlyan alkyl group. Representative examples of alkylamino groups include,but are not limited to, methylamino, (1-methylethyl)amino, methylamino,dimethylamino, methylethylamino, and di(1-methyethyl)amino.

The term “hydroxyalkyl” means an alkyl radical as defined herein,substituted with one or more, preferably one, two or three hydroxygroups. Representative examples of hydroxyalkyl include, but are notlimited to, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl,3-hydroxypropyl, 1-(hydroxymethyl)-2-methylpropyl, 2-hydroxybutyl,3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl,2-hydroxy-1-hydroxymethylethyl, 2,3-dihydroxybutyl, 3,4-dihydroxybutyland 2-(hydroxymethyl)-3-hydroxy-propyl, preferably 2-hydroxyethyl,2,3-dihydroxypropyl, and 1-(hydroxymethyl)2-hydroxyethyl.

The term “alkoxy,” as used herein, refers the radical —OR_(x). Exemplaryalkoxy groups include, but are not limited to, methoxy, ethoxy, andpropoxy.

“Aromatic” or “aromatic group” refers to aryl or heteroaryl.

“Aryl” refers to optionally substituted carbocyclic aromatic groups. Insome embodiments, the aryl group includes phenyl, biphenyl, naphthyl,substituted phenyl, substituted biphenyl or substituted naphthyl. Inother embodiments, the aryl group is phenyl or substituted phenyl.

“Aralkyl” refers to an alkyl group which is substituted with an arylgroup. Some non-limiting examples of aralkyl include benzyl andphenethyl.

“Acyl” refers to a monovalent group of the formula —C(═O)H,—C(═O)-alkyl, —C(═O)—aryl, —C(═O)-aralkyl, or —C(═O)-alkaryl.

“Halogen” refers to fluorine, chlorine, bromine and iodine.

“Styryl” refers to a univalent radical C₆H₅—CH═CH— derived from styrene.

“Substituted” as used herein to describe a compound or chemical moietyrefers to that at least one hydrogen atom of that compound or chemicalmoiety is replaced with a second chemical moiety. Non-limiting examplesof substituents are those found in the exemplary compounds andembodiments disclosed herein, as well as halogen; alkyl; heteroalkyl;alkenyl; alkynyl; aryl; heteroaryl; hydroxy; alkoxyl; amino; nitro;thiol; thioether; imine; cyano; amido; phosphonato; phosphine; carboxyl;thiocarbonyl; sulfonyl; sulfonamide; ketone; aldehyde; ester; oxo;haloalkyl (e.g., trifluoromethyl); carbocyclic cycloalkyl, which can bemonocyclic or fused or non-fused polycyclic (e.g., cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl) or a heterocycloalkyl, which canbe monocyclic or fused or non-fused polycyclic (e.g., pyrrolidinyl,piperidinyl, piperazinyl, morpholinyl or thiazinyl); carbocyclic orheterocyclic, monocyclic or fused or non-fused polycyclic aryl (e.g.,phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thiophenyl, imidazolyl,oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl,pyridinyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl,pyrimidinyl, benzimidazolyl, benzothiophenyl or benzofuranyl); amino(primary, secondary or tertiary); o-lower alkyl; o-aryl, aryl;aryl-lower alkyl; —CO₂CH₃; —CONH₂; —OCH₂CONH₂; —NH₂; —SO₂NH₂; —OCHF₂;—CF₃; —OCF₃; —NH(alkyl); —N(alkyl)₂; —NH(aryl); —N(alkyl)(aryl);—N(aryl)₂; —CHO; —CO(alkyl); —CO(aryl); —CO₂(alkyl); and —CO₂(aryl); andsuch moieties can also be optionally substituted by a fused-ringstructure or bridge, for example —OCH₂O—. These substituents canoptionally be further substituted with a substituent selected from suchgroups. All chemical groups disclosed herein can be substituted, unlessit is specified otherwise. For example, “substituted” alkyl, alkenyl,alkynyl, aryl, hydrocarbyl or heterocyclo moieties described herein aremoieties which are substituted with a hydrocarbyl moiety, a substitutedhydrocarbyl moiety, a heteroatom, or a heterocyclo. Further,substituents may include moieties in which a carbon atom is substitutedwith a heteroatom such as nitrogen, oxygen, silicon, phosphorus, boron,sulfur, or a halogen atom. These substituents may include halogen,heterocyclo, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protectedhydroxy, keto, acyl, acyloxy, nitro, amino, amido, cyano, thiol, ketals,acetals, esters and ethers.

In one aspect, the invention provides platinum(II) emitters. In oneembodiment, an organometallic emitter represented by Structure I isprovided. The platinum center in Structure I is in +2 oxidation stateand has a square planar geometry. The coordination sites of the platinumcenter are occupied by a tetradentate ligand. The tetradentate ligandfeaturing with 6-5-6 fused membered rings coordinates to the platinumcenter through a metal-oxygen bond, a nitrogen donor bond, ametal-carbon bond and a nitrogen donor bond in a sequence of O, N, C, N(ÔN̂C*N ligand; i.e., 4 connecting covalent bonds (either single ordouble) between ÔN, 3 connecting covalent bonds (either single ordouble) between N̂C, 4 connecting covalent bonds (either single ordouble) between C*N). The metal-oxygen bond is a bond betweendeprotonated phenol or substituted phenol and platinum, the nitrogendonors are from pyridine and/or isoquinoline groups, and themetal-carbon bond is formed by benzene or substituted benzene andplatinum. There must a one carbon atom between the aromatic systems ofC*N of the ÔN̂C*N system. Two different self-quenching reduction groupsare attached in specific position in a specific fashion.

Platinum(II) Emitters

In one embodiment, the platinum(II) emitters have the chemicalstructures of Structure I:

wherein R₁-R₁₃ are independently hydrogen, halogen, hydroxyl, anunsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstitutedaryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro,acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl,carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group.Each pair of adjacent R groups of R₁-R₁₃ can independently form 5-8member ring(s) with 2 or 4 carbon atoms in the phenyl ring(s) showed inStructure I; B and

are self-quenching reduction groups.

In one embodiment, B is connected to the emitter in the positiondepicted in Structure I through a single covalent bond.

In one embodiment, is connect to the emitter in the position depicted inStructure I through two single covalent bonds to the carbon atom betweenthe C*N of the ÔN̂C*N system through a spiro-linkage.

In one embodiment, R₁-R₁₃ is independently hydrogen, halogen, hydroxyl,an unsubstituted alkyl containing from 1 to 10 carbon atoms, asubstituted alkyl containing from 1 to 20 carbon atoms, cycloalkylcontaining from 4 to 20 carbon atoms, an unsubstituted aryl containingfrom 6 to 20 carbon atoms, a substituted aryl containing from 6 to 20carbon atoms, acyl containing from 1 to 20 carbon atoms, alkoxycontaining from 1 to 20 carbon atoms, acyloxy containing from 1 to 20carbon atoms, amino, nitro, acylamino containing from 1 to 20 carbonatoms, aralkyl containing from 1 to 20 carbon atoms, cyano, carboxylcontaining from 1 to 20 carbon atoms, thiol, styryl, aminocarbonylcontaining from 1 to 20 carbon atoms, carbamoyl containing from 1 to 20carbon atoms, aryloxycarbonyl containing from 1 to 20 carbon atoms,phenoxycarbonyl containing from 1 to 20 carbon atoms, or analkoxycarbonyl group containing from 1 to 20 carbon atoms.

B is typically a hydrocarbon group containing 1 to 24 carbon atoms. Forexample, B can be a substituted aryl group. In one embodiment, Bcontains at least one t-butyl group. In another embodiment, B is:

is typically a hydrocarbon group containing 2 to 40 carbon atoms.

can be a substituted aryl group. In one embodiment,

contains at least one benzyl group. In another embodiment, wherein

is:

wherein R₁₄-R₂₁ are independently hydrogen, halogen, hydroxyl, anunsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstitutedaryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro,acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl,carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group.Each pair of adjacent R groups of R₁₄-R₂₁ can independently form 5-8member ring(s) with 2 or 4 carbon atoms in the phenyl ring(s).

In one embodiment, wherein

is:

wherein X is selected from C, N, O, S, P or Si; R₁₄-R₂₁ areindependently hydrogen, halogen, hydroxy, an unsubstituted alkyl, asubstituted alkyl, cycloalkyl, an unsubstituted aryl, a substitutedaryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano,carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl,phenoxycarbonyl, or an alkoxycarbonyl group. Each pair of adjacent Rgroups of R₁₄-R₂₃ can independently form 5-8 member ring(s) with 2 or 4carbon atoms in the phenyl ring(s).

Certain specific, non-limiting examples for the platinum(II) emitterswith structure I are shown as follows:

Preparation of Platinum(II) Emitter

In one embodiment, the platinum(II) emitter with chemical structure ofStructure I can be prepared from a tetradentate ligand with a chemicalstructure of Structure II:

wherein R₁-R₁₃ are independently hydrogen, halogen, hydroxyl, anunsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstitutedaryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro,acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl,carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group.Each pair of adjacent R groups of R₁-R₁₃ can independently form 5-8member ring(s) with 2 or 4 carbon atoms in the phenyl ring(s) showed inStructure I; B and

are self-quenching reduction groups.

Certain specific non-limiting examples of the tetradentate ligand withStructure II are shown below:

In one embodiment, the tetradentate ligand with Structure II can beprepared by a series of reactions depicted in FIG. 1:

According to FIG. 1, Raw Material 5100 is transformed to Intermediate3100 by Reaction 4100 and then reacts with Raw Material 5200 to getIntermediate 3200 by Reaction 4200. Intermediate 3300 is then producedby Intermediate 3200 by Reaction 4300. Through Reaction 4400,Intermediate 3300 is converted to Intermediate 3400.

On the other hand, Intermediate 3500 is prepared reacting Raw Material5300 and Raw Materials 5400 through Reaction 4500. Afterward,Intermediate 3400 reacts with Intermediate 3500 to form the Ligand 2000.Finally, the Emitter 1000 is prepared from the Ligand by Reaction 4700.

In one embodiment, Reaction 4100 is a Grignard Reagent preparationreaction.

In one embodiment, Reaction 4200 is a Grignard Reaction followed bydehydration reaction using concentrated H₂SO₄.

In one embodiment, Reaction 4300 is a Stille coupling reaction.

In one embodiment, Reaction 4400 is reacting the Intermediate withiodine using pyridine as solvent.

In one embodiment, Reaction 4500 is a condensation reaction.

In one embodiment, Reaction 4600 is performed in the presence of excessammonium acetate and a solvent under a reflux condition.

In one embodiment, Reaction 4700 is reacting a ligand with aplatinum(II) salt in the presence of solven(s). In one embodiment, theplatinum(II) salt is potassium tetrachloroplatinate. In anotherembodiment, the solvents are glacial acetic acid and chloroform.

Physical Properties Related to Industrial Applications

There are many standards to be meet before an emitter can be used inindustry, here are the standards that the emitters in current inventionmet.

1. The emitters must have high emission quantum efficiency. In oneembodiment, the emission quantum efficiency of the platinum(II) emitteris higher than 50%. The 6-5-6 fused ring ONC*N core is an importantconfiguration to obtain high emission quantum efficiency. For examplethe emission quantum efficiency of the materials with ONN*C core aredecreased significantly (ϕ<1%).

2. The emitters must have pure red, green or blue emission for displaypanel application. In one embodiment, the platinum(II) emitters showpure green emission with solution emission λ_(max) of 517±3 nm and CIEcoordinates of (0.31±0.02; 0.63±0.02). This can only be achieved byusing a carbon atom at C^(a) location:

Replacing C^(a) by other atom such as nitrogen leading to red-shift inemission, no green emission can be obtained in those materials whichmade them not suitable for display panel application.

3. The emitter must have a short emission lifetime, say less than 10 μs,to reduce triple-triplet annihilation. In one embodiment, the emissionlifetime of the emitter is 5.1 μs or less. This cannot be achieved by asystem of:

The emitters in this system show long emission lifetime of greater than10 μs.

4. The emitter mush have high decomposition and without remainder incrucible after thermal deposition. In one embodiment, the depositiontemperature determined by TGA is larger than 400° C. and does not haveany remainder in crucible after thermal deposition. The 6-5-6 fused ringONC*N core with a carbon atom at the C^(a) position is an importantconfiguration to obtain this property. For example, remainders usuallyappear in the materials with a nitrogen atom at the C^(a) position.

5. The emitters much have self-quenching constant. In one embodiment,the self-quenching constant for the emitter are in the order of 10⁷ dm³mol⁻¹ s⁻¹ or lower, including, but not limited to, lower than in theorder of 7×10⁶, 5×10⁶, 3×10⁶, 10⁶, 7×10⁵, 5×10⁵, 3×10⁵, or 10⁵ dm³ mol⁻¹s⁻¹. This can only achieved by incorporating both B and

groups in the emitter.

6. The emitters must show high efficiency in single host device withoutout-coupling technique. In one embodiment, the device fabricated fromthe emitter in current invention shows maximum efficiency greater than20% (external quantum efficiency).

7. The emitters must show wide doping window. In one embodiment, theemitter shows wide doping window from 2 wt. %-30 wt. % (the deviceefficiency and CIE coordinates of the device are within the rangesdescribed above).

8. The efficiency roll-off of the device fabricated must be low. In oneembodiment, the efficiency roll-off of the device fabricated from theemitter in current invention is less than 10% at 1,000 cd/m².

9. The device must have high brightness in low operation voltage. In oneembodiment, the devices show brightness greater than or equal to 40,000cd/m² at 10 V.

Since the emitters in the current invention do not carry net charge andare soluble in common solvents, various device fabrication methods canbe used in OLED fabrication.

The emitters of the invention can be formed into thin films by vacuumdeposition, spin-coating, inkjet printing or other known fabricationmethods. Different multilayer OLEDs have been fabricated using thecompounds of the present invention as light-emitting material or asdopant in the emitting layer. In general, the OLEDs are comprised on ananode and a cathode, between which are the hole transporting layer,light-emitting layer, and electron transporting or injection layer. Thepresent invention makes use of an additional carrier confinement layerto improve the performance of the devices.

In one embodiment, the OLED is fabricated by vacuum deposition.

In another embodiment, the OLED is fabricated by solution processincluding spin coating and printing.

EXAMPLES

Following are examples that illustrate embodiments for practicing theinvention. These examples should not be construed as limiting. Allpercentages are by weight and all solvent mixture proportions are byvolume unless otherwise noted.

Example 1 Synthesis of Intermediate 3102

To a solution of magnesium (3.3 g, 137 mmol, 1.2 equiv.) and 40 mL ofanhydrous diethyl ether was slowly added Raw Material 511 (41.5 mL, 137mmol, 1.2 equiv.) via dropping funnel under nitrogen atmosphere.Intermediate 3101 was formed after stirring at reflux for 3 hours andused without further purification.

Example 2 Synthesis of Intermediate 3202

To a solution of Raw Material 5202 (30.0 g, 114 mmol, 1.0 equiv.) inanhydrous THF (30 mL) was slowly added the Intermediate 3102 at roomtemperature under nitrogen atmosphere. After complete addition, thereaction mixture was stirred at reflux for 12 hours. The mixture waspoured into a solution containing 5 mL concentrated H₂SO₄, 5 mL aceticanhydride and 90 mL acetic acid. The reaction mixture was stirred at150° C. for 6 hours. The mixture was poured into methanol. Afterfiltration and washing with cool methanol twice, the Intermediate 3202was obtained as pale brown solid (29.0 g, 65%). ¹H NMR (400 MHz, CDCl₃):δ7.36 (t, J=7.9 Hz, 1H), 7.50 (dd, J=7.6 Hz, J=4.8 Hz, 1H), 7.70 (d,J=8.0 Hz, 1H), 7.90 (dt, J=8.0 Hz, J=8.0 Hz, 1H) 8.04 (q, J=8.8 Hz,J=7.9 Hz, 2H), 8.22 (t, J=1.8 Hz, 1H), 8.72 (d, J=5.1 Hz, 1H).

Example 3 Synthesis of Intermediate 3302

Stille coupling was employed for synthesizing Intermediate 3302. To asolution of Intermediate 3302 (29.0 g, 72.8 mmol, 1.0 equiv.),bis(triphenylphosphine)palladium(II) dichloride (5.1 g, 7.2 mmol, 10 mol%), and 80 mL anhydrous toluene was added 1-ethoxyvinyl tributylstannane(39.3 mL, 101.9 mmol, 1.4 equiv.) under nitrogen atmosphere. Thereaction mixture was refluxed for 24 hours. After cooling, HCl (100 mL,12M) was poured into the mixture, and extracted with dichloromethane(3×50 mL). The combined organic layers were washed with H₂O (3×100 mL)and dried over MgSO₄. The solvent was removed under reduced pressure andthe crude compound was purified by column chromatography on SiO₂ usingethyl acetate/hexane mixture (1:9) as eluent to afford Intermediate 3302as light yellow solid (17.1 g, 66%). ¹H NMR (300 MHz, CDCl₃): δ 2.55 (s,3H), 7.00 (d, J=7.9Hz, 1H), 7.13 (t, J=5.2, 1H), 7.48-7.21 (m, 8H), 7.56(d, J=7.6 Hz, 2H), 7.70 (s, 1H), 7.78 (t, J=7.4 Hz, 3H), 8.59 (d, J=4.1Hz, 1H).

Example 4 Synthesis of Intermediate 3402

A reaction mixture containing Intermediate 3302 (16.8 g, 46.4 mmol, 1equiv.), iodine (17.7 g, 69.6 mmol, 1.5 equiv.) and pyridine (30 mL) wasstirred at 150° C. for 2 hours. The mixture was concentrated underreduced pressure and washed with water twice. The Intermediate 3402 wasallowed to re-crystallize in water/methanol mixture and obtained as palebrown solid (13.4 g, 51%). ¹H NMR (400 MHz, CDCl₃): δ6.30 (s, 2H), 7.03(d, J=8.0 Hz, 1H), 7.37-7.29 (m, 3H), 7.47-7.42 (m, 3H), 7.56 (t, J=7.8Hz, 4H), 7.68 (t, J=7.8 Hz, 1H), 7.99-7.93 (m, 3H), 8.21 (t, J=6.7 Hz,2H), 8.60 (d, J=4.6 Hz, 1H), 8.68 (t, J=7.8 Hz, 1H), 8.87 (d, J=5.8 Hz,2H).

Example 5 Synthesis of Intermediate 3502

To a solution of Raw Material 5402 (9.1 g, 41.5 mmol, 1 equiv.), RawMaterial 5302 (5 mL, 41.5 mmol, 1 eq) and 30 mL ethanol was added NaOH(2.5 equiv., 10M). The resultant mixture was stirred at room temperaturefor 48 hours. After neutralization by acetic acid, the crude product wasfiltered and washed with cool ethanol (3×20 mL) to afford Intermediate3502 as yellow solid (10.2 g, 73%). ¹H NMR (400 MHz, CDCl₃): δ1.38 (s,18H), 6.97 (s, 1H), 7.04 (s, 1H), 7.54-7.50 (m, 4H), 7.63 (d, J=15.5 Hz,1H), 7.99-7.94 (m, 2H), 12.87 (s, 1H).

Example 6 Synthesis of Ligand 2002

The reaction mixture containing Intermediate 3502 (10.4 g, 30.8 mmol,1.2 equiv.), Intermediate 3402 (14.6 g, 25.7 mmol, 1.0 equiv.), ammomiumacetate (19.8 g, 257 mmol, 10 equiv.) and glacial acetic acid (100 mL)was refluxed at 175° C. for 24 hours. The crude mixture was extractedwith dichloromethane (3×60 mL). The combined organic phases were washedwith H₂O (3×50 mL) and dried over MgSO₄. The solvent was removed underreduced pressure and the crude compound was purified by columnchromatography on SiO₂ using ethyl acetate/hexane mixture (1:10) aseluent to afford Ligand 2002 as light yellow solid (4 g, 23%). ¹H NMR(600 MHz, CDCl₃): δ 1.40 (s, 18 H, —CH₃), 6.92 (t, J=7.6 Hz, 1H, H⁵),7.04 (d, J=7.4 Hz, 1H, H³), 7.08 (d, J=8.0 Hz, 1H, H¹⁵), 7.13 (t, J=5.6Hz, 1H, H²¹), 7.17 (d, J=8.0 Hz, 1H, H²⁰), 7.32 (t, J=7.0 Hz, 3H, H⁴,H²⁷), 7.39 (q, J=11.3 Hz, J=7.9 Hz, 3H, H¹⁶, H²³, H²⁵), 7.44 (s, 2H,H³¹), 7.48, (t, J=7.8 Hz, 1H, H²²), 7.56 (s, 2H, H¹⁰, H³³), 7.73 (d,J=7.6 Hz, 3H, H²⁶, H¹³), 7.80 (d, J=7.6 Hz, 2H, H²⁵), 7.88 (q, J=8.1 Hz,J=7.1 Hz, 2H, H⁶, H¹⁷), 7.96 (s, 1H, H⁸), 8.70 (s, 1H, H²³), 14.63 (s,1H, —OH).

Example 7 Synthesis of Emitter 1002

A mixture of K₂PtCl₄ (2.9 g, 7.0 mmol, 1.3 equiv.) and the Ligand 2002(3.7 g, 5.4 mmol, 1.0 equiv.) in chloroform (5 mL) and glacial aceticacid (50 mL) was refluxed for 24 hours. The crude mixture wasneutralized by sodium bicarbonate solution and extracted withdichloromethane (3×50 mL). The combined organic layers were washed withH₂O (3×50 mL) and dried over MgSO₄. The solvent was removed underreduced pressure and the crude product was purified by columnchromatography on SiO₂ using ethyl acetate/hexane mixture (2:8) aseluent to afford Emitter 1002 as light yellow solid (1.5 g, 31%). ¹H NMR(600 MHz, CDCl₃): δ1.43 (s, 18H, —CH₃), 6.36 (d, J=7.9 Hz, 1H, H¹⁵),6.78 (t, J=6.9 Hz, 1H, H⁵), 6.85 (t, J=7.7 Hz, 1H, H¹⁶), 6.92 (d, J=8.3Hz, 1H, H²⁰), 7.28-7.30 (m, 3H, H³, H²⁶), 7.38-7.45 (m, 4H, H⁴, H²²,H²⁷), 7.60-7.64 (m, 3H, H¹⁷, H²¹, H³³), 7.65 (s, 2H, H³¹), 7.84 (d,J=7.6 Hz, 2H, H²⁸), 7.89 (s, 1H, H¹⁰), 8.02 (d, J=7.5 Hz, 1H, H⁶), 8.09(d, J=7.7 Hz, 2H, H²⁵), 8.21 (s, 1H, H⁹), 10.40 (s, 1H, H²³). ¹³C NMR(150 MHz, CDCl₃) δ165.13, 164.54, 160.97, 153.30, 152.00, 151.79,150.74, 150.44, 145.50, 140.64, 139.96, 139.01, 137.97, 137.88, 131.42,130.38, 128.50, 128.20, 126.62, 126.27, 125.05, 123.84, 123.80, 123.48,122.95, 122.80, 122.69, 121.45, 120.47, 118.80, 114.84, 113.52. MS(FAB): 867.29[M⁺]. Anal. Calcd for C₄₉H₄₂N₂OPt: C 67.65, H 4.87, N 3.22.Found: C 67.07, H 4.99, N 3.06.

Example 8 Synthesis of Intermediate 3108

To a solution of magnesium (3.3 g, 137 mmol, 1.2 equiv.) and 40 mL ofanhydrous diethyl ether was slowly added Raw Material 5108 (40.5 g, 137mmol, 1.2 equiv.) via dropping funnel under nitrogen atmosphere. TheGrignard reagent was formed after stirring at reflux for overnight andused without purification.

Example 9 Synthesis of Intermediate 3208

To a solution of Raw Material 5208 (30.0 g, 114 mmol, 1.0 equiv.) inanhydrous THF (30 mL) was slowly added Intermediate 3108 at roomtemperature under nitrogen atmosphere. After complete addition, thereaction mixture was stirred at reflux for addition of 12 hours. Themixture was poured into a solution containing 5 mL concentrated H₂SO₄, 5mL acetic anhydride and 90 mL acetic acid. The reaction mixture wasstirred at 150° C. for 12 hours. The mixture was extracted withdichloromethane and combined organic layer was washed with H₂ O anddried over anhydrous MgSO₄. The product was purified by columnchromatography using Hexane:Ethyl Acetate (8:2) as eluent. The compoundwas obtained as pale white solid (35.6 g, 63%). ¹H NMR (400 MHz, CDCl₃):δ 6.79 (d, J=8.0 Hz, 1H), 6.96-7.03 (m, 6H), 7.07 (t, J=7.9 Hz, 1H),7.13 (d, J=8.1 Hz, 2H) 7.18-7.22 (m, 3H), 7.31 (d, J=7.2 Hz, 1H), 7.42(t, J=5.86 Hz, 1H), 8.56 (d, J=4.7 Hz, 1H).

Example 10 Synthesis of Intermediate 3308

To a solution of Intermediate 3208 (35.6 g, 86.3 mmol, 1.0 equiv.),bis(triphenylphosphine)palladium(II) dichloride (6.1 g, 8.6 mmol, 10 mol%), and 80 mL anhydrous toluene was added 1-ethoxyvinyl tributylstannane(39.3 mL, 101.9 mmol, 1.2 equiv.) under nitrogen atmosphere. Thereaction mixture was refluxed for 48 hours. After cooling, HCl (100 mL,12M) was poured into the mixture, and extracted with dichloromethane(3×50 mL). The combined organic layers were washed with H₂O (3×100 mL)and dried over MgSO₄. The solvent was removed under reduced pressure andthe crude compound was purified by column chromatography on SiO₂ usingethyl acetate/hexane mixture (1:9) as eluent to afford Intermediate 3308as light yellow solid (19.5 g, 65%). ¹H NMR (400 MHz, CDCl₃): δ 2.45 (s,3H), 6.83 (d, J=7.6Hz, 1H), 6.97-7.01(m, 4H), 7.12 (t, J=7.6 Hz, 1H),7.15 (d, J=8.0Hz, 2H), 7.23-7.28 (m, 3H), 7.34 (t, J=7.8 Hz, 1H), 7.67(s, 1H), 7.8 (d, J=4.8 Hz, 1H) 8.6 (d, J=4.1 Hz, 1H).

Example 11 Synthesis of Intermediate 3408

A reaction mixture containing Intermediate 3380 (19.5 g, 51.8 mmol, 1equiv.), iodine (17.7 g, 69.6 mmol, 1.3 equiv.) and pyridine (30 mL) wasstirred at 150° C. for 8 hours. The mixture was concentrated underreduced pressure. Intermediate 3408 was used for the next step withoutpurification.

Example 12 Synthesis of Ligand 2008

The reaction mixture containing Intermediate 3502 (1.4 g, 4.1 mmol, 1.2equiv.), Intermediate 3408 (2 g, 3.4 mmol, 1.0 equiv.), ammomium acetate(2.6 g, 34.0 mmol, 10 equiv.) and glacial acetic acid (100 mL) wasrefluxed at 175° C. for 24 hours. The crude mixture was extracted withdichloromethane (3×60 mL). The combined organic phases were washed withH₂O (3×50 mL) and dried over MgSO₄. The crude product was purified bycolumn chromatography on SiO₂ using ethyl acetate/hexane mixture (1:10)as eluent to afford Ligand 2008 as yellow solid (1.1 g, 47%). ¹H NMR(300 MHz, CDCl₃): δ 1.31 (s, 18H, —CH₃), 6.85-7.01 (m, 7H), 7.03-7.09(m, 4H), 7.17-7.23 (m, 4H), 7.35-7.40 (m, 3H), 7.48-7.54 (m, 3H), 7.60(s, 1H), 7.83 (q, J=6.8 Hz, J=8.0 Hz, 2H), 7.94 (s, 1H), 8.53 (d, J=3.9Hz, 1H) 14.21 (s, 1H, —OH).

Example 13 Synthesis of Emitter 1008

A mixture of K₂PtCl₄ (0.9 g, 2.1 mmol, 1.3 equiv.) and the Ligand 2008(1.1 g, 1.6 mmol, 1.0 equiv.) in chloroform (5 mL) and glacial aceticacid (50 mL) was refluxed for 24 hours. The solvent was removed underreduced pressure and the crude product was purified by columnchromatography on SiO₂ using ethyl acetate/hexane mixture (2:8) aseluent to afford Emitter 1008 as light yellow solid (0.38 g, 38%). ¹HNMR (600 MHz, CD₂Cl₂): δ 0.66-0.82 (m, 10H), 1.08-1.17 (m, 4H),2.02-2.10 (m, 4H), 6.70-6.73 (m, 2H), 6.81-6.85 (m, 2H), 6.96 (t, J=7.6Hz, 1H), 7.16-7.32 (m, 8H), 7.51 (t, J=7.5 Hz, 2H), 7.56 (d, J=7.7 Hz,1H), 7.67 (t, J=6.7 Hz, 1H), 7.83 (d, J=7.7 Hz, 1h), 10.73 (s, 1H).

Example 14 X-Ray Diffraction Data of Emitter 1002

The structure is depicted in FIG. 2 which shows the emitter is not inplanar structure. X-Ray diffraction data of single crystals werecollected on a MAR PSD diffractometer with a 300 mm image plate detectoror Bruker X8 Proteum diffractometer. The diffraction images wereinterpreted and diffraction intensities were integrated using programDENZO and the crystal structures were solved by direct methods employingSHELXS-97 program.

Formula C₄₉H₄₂N₂OPt Temperature, K 100 Formula weight 869.29 Crystalsystem triclinic Space group P -1 a, Å 12.4607(5) b, Å 12.7920(5) c, Å14.1587(6) α, deg  67.97(1) β, deg  85.66(1) γ, deg  68.67(1) Cellvolume, Å³  1944.0(14) Z 1 Density, calculated, 1.588 g/cm³, mm⁻¹ 8.013Index ranges h = −14→13 k = −15→15  i = −16→15 F(000) 930 Theta range,deg 3.4-66.1 R₁ 0.0439 wR₂ 0.1182 GoF 1.097 largest diff. peak/hole [eÅ⁻³] 2.46/−1.42 Note : R₁ = Σ||F_(o)| − |F_(c)||/Σ|F_(o)|, wR₂ ={Σ[w(F_(o) ² − F_(c) ²)²]/Σ[w(F_(o) ²)²]}^(1/2)

Example 15 Physical Data for Emitter 1002

The UV-Vis absorption and emission spectra of Emitter 1002 is depictedin FIG. 3.

UV-Vis absorption^([a]) Emission^([a]) λ_(max)[nm] k_(q) ^([c]) (ε[mol⁻¹dm³ λ_(max)[nm] [mol⁻¹dm³ HOMO LUMO cm⁻¹]) (τ [μs]) Φ_(em) ^([b])s⁻¹] [eV] ^([d]) [eV] ^([d]) 261 (49763), 279 517 0.80 1.1 × 10⁷ −5.3−2.6 (54453), 301 (5.10), (36052), 329 535 (17799), 356 (5.10) (17400),393 (7227), 431 (3826) ^([a])Determined in degassed CH₂Cl₂ (2 × 10⁻⁵ moldm⁻³). ^([b]) Emission quantum yield was esitmated with BPEA(9,10-bis(phenylethynyl)anthracene) in degassed CH₃CN as standard(Φ_(em) = 0.85). ^([c]) Self-quenching constant. ^([e]) The HOMO andLUMO levels were estimated from onset potentials in cyclic voltammerystudy using Cp₂Fe^(0/+) value of 4.8 eV below the vacuum level.

Example 15 Key Performance of OLEDs Fabricated from Emitter 1002

All OLEDs were constructed with a simple architecture of ITO/MoO₃ (5nm)/HTL (50 nm)/TCTA: Emitter 1002 (10 nm)/ETL (50 nm)/LiF (1.2 nm)/Al(150 nm). TAPC (di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane) was usedas the hole-transporting layer (HTL) while TmPyPB(1,3,5-tri(m-pyrid-3-yl-phenyl)) or Tm3PyBPZ(2,4,6-tris(3-(3-(pyridin-3-yl) phenyl) phenyl)-1,3,5-triazine) as theelectron-transporting layer (ETL).

EQE^(f)) (%) L^(b)) Max. at at (cd V_(on) ^(d)) PE^(e)) 1000 10000CIE^(g)) C^(a)) m⁻²) (V) (lm/W) Max. cd m⁻² cd m⁻² (x, y)  2 wt % ^(h))19000 2.9 99.6 24.9 20.4 9.59 (0.29, 0.64)  6 wt % ^(h)) 40000 2.8 106.726.9 26.2 19.1 (0.31, 0.64) 10 wt % ^(h)) 47000 2.7 109.4 27.6 25.6 20.0(0.31, 0.64) 30 wt % ^(h)) 49700 2.7 95.7 24.0 21.9 17.9 (0.33, 0.63) 10wt)^(i)) 35300 2.4 126 26.4 23.4 13.6 (0.31, 0.63) ^(a))dopingconcentration; ^(b))luminance at 12 V; ^(c))luminance at 10 V;^(d))turn-on voltage: the driving voltage at luminance ~1 cd m⁻²;^(e))Power efficiency; ^(f))external quantum efficiency; ^(g))CIEcoordinates at 1000 cd m⁻²; ^(h)) TmPyPb is used as theelectron-transporting layer. ^(i))Tm3PyBPZ is used as theelectron-transporting layer.

The graphs are depicted in FIG. 4-FIG. 8.

Example 16 Theory Calculation and Femtosecond Time-Resolved FluorescentMeasurements

To account for the high efficiency and low efficiency roll-off ofEmitter 1002 OLEDs, theory calculations and femtosecond time-resolvedfluorescence measurements have been performed. TDDFT calculations atM062X/6-311G*(|an|2dz) level based on the geometries of triplet excitedstates of Emitter 1002 give emission wavelength of 512 nm, which is inagreement with the experimental data (517 nm). As expected, for Emitter1002, the geometrical differences between T₁ and S₀ states are verysmall, which means very slow non-radiative decay rate constants (k_(nr))of T₁ to S₀. The optimized geometries of Emitter 1002 dimmers are shownin FIG. 9. The calculated geometrical parameters are in good agreementwith the X-ray crystallography data.

The Pt—Pt distances is 4.616 Å, no Pt—Pt interactions arise.

The HOMO and LUMO are mainly localized on the ÔN̂ĈN ligand (see FIG. 10).

The emission is mainly from HOMO-1→LUMO+1 (81.4%), which is mainlyattributed to the π-π* transition of the substituent of the ligand.

Femtosecond time-resolved fluorescence measurement with CH₂Cl₂ solutionof Emitter 1002 (λ_(max)=350 nm) revealed fluorescence (FIGS. 11) thatdecays with time constant of −0.15 ps. This extremely rapid decay offluorescence is suggestive of the presence of nearly unitary efficiencynonradiative decay attributed to efficient ISC from the electronicallyexcited singlet to give the triplet states.

With respect to any figure or numerical range for a givencharacteristic, a figure or a parameter from one range may be combinedwith another figure or a parameter from a different range for the samecharacteristic to generate a numerical range.

Other than in the operating examples, or where otherwise indicated, allnumbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used in the specification andclaims are to be understood as modified in all instances by the term“about.”

While the invention has been explained in relation to certainembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

What is claimed is:
 1. An organic light-emitting diode (OLED) emitterhaving a chemical structure of Structure I:

wherein R₁-R₁₃ are independently hydrogen, halogen, hydroxyl, anunsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstitutedaryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro,acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl,carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group,each pair of adjacent R groups of R₁-R₁₃ can independently join togetherto form a 5-8 member ring(s); wherein B is a hydrocarbon groupcontaining 1 to 24 carbon atoms or a substituted aryl group; and wherein

is a spiro-linkage.
 2. The OLED emitter in claim 1, wherein thespiro-linkage is:

wherein R₁₄-R₂₁ are independently hydrogen, halogen, hydroxyl, anunsubstituted alkyl, a substituted alkyl, cycloalkyl, an unsubstitutedaryl, a substituted aryl, acyl, alkoxy, acyloxy, amino, nitro,acylamino, aralkyl, cyano, carboxyl, thio, styryl, aminocarbonyl,carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or an alkoxycarbonyl group,each pair of adjacent R groups of R₁₄-R₂₁ can independently form 5-8member ring(s) with 2 or 4 carbon atoms in the phenyl ring(s).
 3. TheOLED emitter in claim 1, wherein the spiro-linkage is:

wherein X is selected from C, N, O, S, P or Si; R₁₄-R₂₁ areindependently hydrogen, halogen, hydroxy, an unsubstituted alkyl, asubstituted alkyl, cycloalkyl, an unsubstituted aryl, a substitutedaryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano,carboxyl, thio, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl,phenoxycarbonyl, or an alkoxycarbonyl group, each pair of adjacent Rgroups of R₁₄-R₂₁ can independently form 5-8 member ring(s) with 2 or 4carbon atoms in the phenyl ring(s).
 4. The OLED emitter in claim 1,wherein the spiro-linkage comprises a substituted aryl group.
 5. TheOLED emitter in claim 1, wherein the spiro-linkage comprises at leastone benzyl group.
 6. The OLED emitter in claim 1, wherein each R₁-R₁₃ isindependently hydrogen, halogen, hydroxyl, an unsubstituted alkylcontaining from 1 to 10 carbon atoms, a substituted alkyl containingfrom 1 to 20 carbon atoms, cycloalkyl containing from 4 to 20 carbonatoms, an unsubstituted aryl containing from 6 to 20 carbon atoms, asubstituted aryl containing from 6 to 20 carbon atoms, acyl containingfrom 1 to 20 carbon atoms, alkoxy containing from 1 to 20 carbon atoms,acyloxy containing from 1 to 20 carbon atoms, amino, nitro, acylaminocontaining from 1 to 20 carbon atoms, aralkyl containing from 1 to 20carbon atoms, cyano, carboxyl containing from 1 to 20 carbon atoms,thiol, styryl, aminocarbonyl containing from 1 to 20 carbon atoms,carbamoyl containing from 1 to 20 carbon atoms, aryloxycarbonylcontaining from 1 to 20 carbon atoms, phenoxycarbonyl containing from 1to 20 carbon atoms, or an alkoxycarbonyl group containing from 1 to 20carbon atoms.
 7. The OLED emitter in claim 1, wherein B is:


8. The OLED emitter in claim 1 having a green emission in dilutesolution with emission λ_(max)<520 nm.
 9. The OLED emitter in claim 1having a short emission lifetime of less than 6 μs.
 10. The OLED emitterin claim 1 having a self-quenching constant in the order of below 10⁻⁷dm³ mol⁻¹ s⁻¹.
 11. A light-emitting device comprising at least one OLEDemitter of claim 1 as an emitting material.
 12. The light-emittingdevice of claim 11, wherein the device is an organic light-emittingdiode (OLED).
 13. The light-emitting device of claim 11, wherein thedevice is fabricated by vacuum deposition.
 14. The light-emitting deviceof claim 11, wherein the device is fabricated by solution processes. 15.The light-emitting device of claim 11, wherein the device contains oneemissive layer.
 16. The light-emitting device of claim 11, wherein thedevice contains more than one emissive layer.
 17. The light-emittingdevice of claim 11, wherein the efficiency roll-off at 1000 cd/m⁻² isless than 10%.
 18. The light-emitting device of claim 11, wherein thedoping concentration of the emitter is from 2-30 weight % withoutchanging the emitting color (change of CIEx less than 0.03 and or changeof CIEy less than 0.02).